Process for the manufacture of polyurethane plastics



g- 1958 P. HOPPE ETAL Re. 24,514

PROCESS FOR THE MANUFACTURE OF POLYURETHANE PLASTICS R Original Filed Aug. 8, 1955 1 s Sheets-Sheet 1 Au 12, 1958 P. HOPPEETAL v Re. 24,514

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United States Patent Re. 24,514 Rciesueti Aug. 12, 1958 PROCESS FOR THE. MANUFACTURE OF POLYURETHi'aNE PLASTICS Peter, Hoppe, Troisdorf, and Erwin Weinbrenner and Cornelius Miihlhausen, Leverkusen-Bayerwerk, and Karl Breer, Koln-Flittard, Germany, assignors, by direct and mesne assignments, of one-half to Farhcnfabriken Bayer Aktiengesellschaft, Leverkusen-Bayer werk, Germany, a corporation of Germany, and onehalf to 'Mobay Chemical Company, St. Louis, Mm, a corporation of Delaware Original No. 2,764,565, dated September 25, 1956, Serial No. 527,106, August 8, 1955. Application for reissue July 18, 1957, Serial No. 675,793

Claims priority, application Germany December 24, 1951 39 claims.

This invention relates to an improved process and apparatus for the manufacture of porous and homogeneous polyurethane plastics of rigid, semi-rigid or elastic consistency. The application is a continuation-in-part of our copending application Serial No. 327,522, filed December 23, 1952.

The formation of polyurethane plastics involves essentiallya polyaddition between polyesters and polyisocyanates although, in compounding to obtain the final products, other materials, such as fillers, accelerators and/ or cross-linking agents are desirably added. When foamed products are sought, Water or an aqueous solution may also be employed. The plastic materials having a specific gravity of about 0.021.0 are porous and are classified as foamed plastics; those Which have a specific gravity of about 1.0-1.4 are non-porous and are designated as homogeneous plastics.

The process of the invention involves a complex series of physical-chemical reactions wherein heat is evolved, viscosity changes are effected and rapid and uniform mixing of materials of widely difierent viscosities is necessary. By proceeding according to the present invention, applicants have been able to control these conditions to a degree heretofore unattainable and products may be produced which are not subject to the deficiencies of the prior art but are uniform in texture and reproducible in quality. Thus, in contrast to the prior art products, the plastics of the present invention are more uniform in appearance, have a more regular cell structure and are reproducible to a high degree. Shrinkage after curing (i. e., within a few minutes after the initial foam rise has been completed) which is a primary problem in the manufacture of light foams is held to a minimum as a result of the present invention. Whereas it was considered essential to mix the components necessary for formation of the polyurethane plastics for several minutes in the prior art processes, the process of the invention (carried out in the apparatus invented therefor) normally requires a mixing time of the order 0.5 to seconds.

In the formation of polyurethane plastics by the process of the instant invention, the condensation of polyesters and polyisocyanates is carried out in the presence of an activator mixture (the term activator mixture, as used herein, is meant to include at least one accelerator and/or cross-linking agent to which may be added water or an aqueous solution, if necessary). The activator mixture is introduced into the reaction mixture in a fine state of subdivision at an elevated pressure substantially higher than that of the reactant mixture. components is effected in an enclosed vessel for a short period of time, and the resultant product is discharged while still in the liquid state and before any substantial liberation of gases has taken place. It is preferred to introduce the activator mixture into the polyester-polyisocyanate intermittently for most effective operation, However, it is possible to control conditions so that, in certain operations, a continuous feed for this component may be utilized. The activator mixture is introduced into the polyester-polyisocyanate shortly before the polyacldition reaction takes place; and the cross-linking action and/or foaming of the polyurethanes thereby becomes one of extremely high intensity and yields a more homogeneous product for use in the manufacture of moldings, cavity fillings, coatings, piece goods, etc.

The expression component influencing the reaction, as hereinafter used comprises the activator mixture defined above and/or any other material or combination of materials having a catalytic effect on the reaction between the polyisocyanate and the other reactants used in the manufacture of homogeneous and porous plastics.

Thus, in the process of the invention, an hydroxy polyester, a polyis-ocyanate and a component influencing the reaction are brought together in a mixing zone, with at least the reaction influencing component being injected at a pressure substantially higher than the back pressure in the mixing zone and then discharging the resulting uniform mixture of ingredients in the liquid state from said zone. The polyester and polyisocyanate may be introduced into the mixing zone either separately or inadmixture; and the reaction influencing component may be introduced separately, or if desired, in admixture with the polyester or the polyisocyanate provided the latter is used in a blocked or inactive form which liberates the polyisocyanate on heating. Polyisocyanate-modified polyesters, polyesteramides, polyisocyanate-modified polyesteramides, alkylcne glycols, polyisocyanate-modified alkylene glycols, polyoxyalkylene glycols, and polyisocyanate-modified polyoxyalkylene glycols may also be utilized in the process.

The polyesters used for the production of the polyurethanes having a specific gravity in the range of about 0.02l.4 (i. e. those of rigid, semi-rigid or elastic consistency) may be branched and/or linear. Thus, the useful polyesters and/or polyesteramides may include those obtained by condensing any polybasic (preferably dibasic carboxylic) organic acid, such as adipic, sebacic, 6-arnino-caproic, phthalic, isophthalic, terphthalic, oxalic, malonic, succinic, maleic, cyclohexane-l,Z-dicarboxylic, cyclohexane-l,4-dicarboxylic, polyacrylic, naphthalene- LZ-dicarboxylic, fumaric, itaconic, etc., with polyalcohols such as ethylene glycol, diethylene glycol, pentag'lycol, glycerol, sorbitol, trietholamine, di (fl-hydroxyethyl) ether, etc. and/ or amino-alcohols such as ethanolamine, 3-aminopropanol, 4-aminopropanol, S-aminopentanol-l, 6-aminohexanol, IO-amino-decanol, 6-amino-5-methylhexanol-l, p-hydroxymethylbenzylamine, etc.; and with mixtures of the above polyalcohols and amines, ethylene diamine, hexamethylene diamine, 3-methylhexamethylene diamine, decamethylene diamine and m-phenylenediamine, etc.) and/or amino-alcohols, etc. In the esterification, the acid per se may be used for condensation or, where desirable, equivalent components, such as the acid halide or anhydride may be used.

The alkylene glycols and polyoxyalkylene glycols used in the practice of the invention may comprise ethylene glycol, propylene glycol, butylene glycol-2,3; butylene glycol- 1,3; Z-methyl pentanediol2,4; 2-ethylhexanediol- 1,3; hexamethylene glycol, styrene glycol and decamethyl- Mixing of the,

.J ene glycol, etc. and diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols 200, 400 and 600 etc. dipropylene glycol, tripropylene glycol, polypropylene glycols 400, 750, 1,200 and 2,000 etc.

Broadly, any of the prior art polyesters, polyisocyanatemodified polyesters, polyesteramides, polyisocyanatemodified polyesteramides, alkylene glycols, polyisocyanate-modified alkylene glycols, polyoxyalkylene glycols and polyisocyanate-modified polyoxyalkylene glycols, etc. having free reactive hydrogen atoms, free reactive carboxylic and/or especially hydroxyl groups may be employed in the process of the invention and condensed in the apparatus useful for carrying out that process. Moreover, any organic compound containing at least two radicals selected from the class consisting of hydroxyl and carboxyl groups may be employed in the practice of the invention.

The organic polyisocyanates useful in the practice of the invention include ethylene diisocyanate, ethylidene diisocyanate, propylene 1,2 diisocyanate, butylene-1,3-diisocyanate, hexylene-1,6-diisocyanate, cyclohexylene-l,2- diisocyanate, m-phenylene diisocyanate, 2,4-toluylene diisocyanate, 1,6-toluylene diisocyanate, 3,3-dimethyl-4,4- biphenylene diisocyanate, 3,3 dimethoxy-4,4-biphenylene diisocyanate, 3,3'-diphenyl-4,4'-biphenylene diisocyanate, 4,4-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, triphenylmethane triisocyanate, 1,5-naphthalene diisocyanate or polyisocyanates in a blocked or inactive form such as the bis-phenyl carbamates of toluylene diisocyanate, p,p-diphenylmethane diisocyanate, p-phenylene diisocyanate and Lil-naphthalene diiso cyanate, etc.

The activator mixture is made up of at least one crosslinking agent and/ or an accelerator and may contain, if desired, added water or an aqueous solution. The addition of such an activator mixture to the mixture of poly isocyanates and polyesters initiates the cross-linking action needed to obtain homogeneous plastics or the cross-linking and foaming action necessary to obtain foam plastics.

Useful cross-linking agents include water or aqueous solu' 'tions for foamed plastics and the polyalcohols, such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, glycerol, etc. for non-porous plastics; and useful accelerators include the tertiary amines (either individually or in mixture) such as dirnethylhexahydroaniline, diethylhexahydroaniline, reaction products of N,N'-diethylaminoethanol and phenylisocyanate, esteramines, etc. Also sodium phenolates, added with suitable plasticizers, may be employed in the manufacture of foamed products.

As has been indicated above, it is desirable and advantageous to introduce the activator mixture, in a very fine state of subdivision and under relatively high pressure, into the polyester-polyisocyanate mixture before polyaddition occurs. The required amount of activator mixture, which is small compared with the other components, is injected into the mixture of isocyanate and polyester under high pressure and preferably by means of one or more injection nozzles and intermittently operating pumps, for instance by means of the devices hereinafter described.

According to one embodiment of the invention, the activator mixture is introduced or injected intermittently into a continuous stream of polyisocyanate and polyester, which stream is advanced by standard means such as a gear pump system. To insure adequate penetration of the activator mixture into the reaction mixture, the intermittent feed enters through a nozzle or nozzles at a relatively high pressure and frequency.

To carry out the above described process, an apparatus is employed which includes an enclosed reaction or mixing device, means for inducing continuous flow of initial materials such as the isocyana'te-polyester mixture and means for intermittently introducing the activator mixture into the reaction mixture at elevated pressure. More particularly, the apparatus preferably includes at least one injection device to efiect the proper intermittent feed of the activator mixture through a nozzle or another suitable device into the continuous stream of the initial materials.

In a preferred embodiment of the invention, the two reaction components of the reaction mixture, namely at least one diisocyanate and at least one polyester containing hydroxyl groups, are conveyed separately to a reaction or mixing device into which they are injected under pressure through separate nozzles or a common mixing nozzle and the activator mixture is either conveyed separately to the reaction device and injected into it under pressure through a separate nozzle or a common mixing nozzle.

The activator mixture may advantageously be conveyed to the reaction or mixing device in admixture with the polyester component, the mixture being injected under pressure into the device either through a common mixing nozzle with the isocyanate component or through a separate nozzle. Similarly, in some operations, particularly in the production of homogeneous plastics, the activator mixture may be conveyed to the reaction or mixing device in admixture with the polyisocyanate if the latter is employed in a blocked or inactive form which liberates the polyisocyanate on heating.

In the practice of the invention in its preferred form, the components employed in the manufacture of the plastic are forced into a common reaction or mixing device by means of pumps. One of the pumps operates continuously while the other pumps operate intermittently; all of the pumps are connected to the reaction or mixing device into which one component is introduced continuously While the activator mixture or preferably the activator mixture and the polyisccyanate areintroduced intermittently. The components conveyed by the pumps are introduced by means of nozzles into the reaction or mixing device which has outlet means through which the final mixture is discharged in the liquid state.

Broadly stated, the apparatus of the invention comprises, in combination, an enclosed mixer and means through which the components (i. e. polyester containing free hydroxyl groups, polyisocyanate and reaction in fluencing component) used in the manufacture of the plastics are brought together in said mixer, at least one of said means comprising an injector operating at a pressure substantially higher than that in said mixer, and outlet means through which the final uniform mixture of components is discharged in the liquid state.

More specifically, the apparatus for carrying out the process of the invention comprises, in combination, an enclosed mixer, means to effect a continuous how of initial materials (polyisocyanate and polyester or polyisocyanate-modified' polyester) to the mixer, means for feeding the activator mixture and/or polyisocyanate and means for intermittently injecting the activator mixture and/or polyisocyanate in precise quantities into a continuous stream of the initial materials by means of at least one injection nozzle. Still more specifically, the apparatus includes a similar combination of elements together With means for separately and intermittently injecting the polyisocyanate and the activator mixture under pressure into a continuous stream of the initial material by means of injection nozzles.

The initial material or materials and the accelerator mixture are generally stored in tanks and are conveyed to the reaction or mixing device by means of pumps which, as indicated above, operate continuously but preferably intermittently in the case of the accelerator and/ or the polyisocyanate. Any other standard method of storing and transfering the materials to the reaction or mixing device may be used.

The reaction or mixing device may contain separate compartments or chambers for injection of the reaction components and mixing. It is possible, however, to arrange the device so that both injection and mixing are carried out in a single compartment.

a ibi In the single chamber apparatus, the components conveyed by the pumps are fed (the polyester preferably by continuous flow; the accelerator mixture and polyisocyanate preferably by intermittent injection) through nozzles into a chamber equipped with stirring means (e. g. a mechanical stirrer) as well as outlet means through which the final mixture is discharged in the liquid state. In another embodiment of the single chamber apparatus (see Fig. 3), the components conveyed by the pumps are forced (the mixture of polyisocyanate and polyester in continuous flow and the accelerator mixture by intermittent injection) through nozzles into an injection chamber provided with outlet means through which the final mixture is discharged in the liquid state.

Where a 2-compartment device is used, one or more of the reaction components required to form the desired plastic is introduced into the injection chamber continuously while another component including the activator mixture is intermittently injected into the continuous flow of the other components. Further mixing is then effected in a separate chamber by a desirable stirring means.

According to one embodiment of the two chamber appav ratus of the invention, the reaction or mixing device is divided by means of a nozzle plate into the injection chamber wherein the components are added and partially mixed and the mixing chamber wherein a more thorough mixing is effected. Any suitable stirring means may be used for this purpose. Thus, the mixing chamber may be provided with a tangential air feed connection through which compressed air is introduced into the mixing chamber to effect a turbulent flow and thorough mixing of the components. Alternatively the apparatus may be divided by a nozzle plate into one compartment equipped with a mechanical stirrer and another compartment provided with a tangential air pipe connection for compressed air stirring.

The mixing time may be varied depending on the proportions and character of the components employed as well as the type of plastic desired. Normally the mixing time is in the range of 0.5-25 seconds, although longer or even shorter mixing periods may in some cases be desirable. The final reaction mixture, in the liquid state, may be treated in various manners. For example, it may be passed onto a screw conveyor which forces the mixture through appropriately shaped nozzles to produce moldings of any desired design or insulating coverings for cables. Sometimes it is desirable to complete and/ or accelerate the reaction of the liquid mixture issuing from the mixing chamber by heating. And this, of course, may be done.

To the polyisocyanates one may add, in anhydrous condition, oils such as paraffin oils (or other mineral oils) or surface-active substances to serve as activators for facilitating the feeding of the isocyanate. Such oils may also be added to one or more of the other components used in the formation of the plastics. These oils affect the porosity and/0r density of the final product, which may be varied by varying the quantity of anhydrous oil added.

For continuous or conveyor belt manufacture of plastics, foamed products or foils, the apparatus of the invention may be made up essentially of storage means (i. e. a storage tank) and a metering pump mounted on a stationary support; and two similar storage means attached to metering pumps mounted on an oscillating casting carriage which moves transversely to the conveyor belt. The components are injected through nozzles by means of the pumps into the reaction or mixing device which is mounted on the oscillating casting carriage.

For the production of foils the carriage moves transversely to the conveyor belt which slowly travels transversely to the moving direction of the casting carriage.

For the production of moldings the liquid mixture issuing from the mixing chamber is cast into molds arranged and positioned on a turntable. The discharge of the mixture from the. mixing..chamber is controlled and adjusted in proper relation to the travelling velocity of the molds. In the continuous manufacture of profile cords or hollow articles for the coating of wire or similar hollow articles the mixture issuing from the mixing chamber is introduced into a conveyor screw which forces the almost completelyreacted material through appropriately shaped profile nozzles. After issuing from the mixing chamber, the material is passed into a chamber Where it is hardened by completing the reaction. The product is then Wound up on a roller.

The apparatus according to the invention can be adapted for instance for the manufacture of porous and homogeneous plastics having a basis of polyurethanes. The apparatus for carrying into effect this embodiment of the invention consists essentially of a pump for inducing continuous flow of the initial material, e. g. a mixture of a polyisocyanate anda polyester, and another pump intermittently feeding the activator component, e. g. tertiary amines, into the continuous stream of the initial material. The continuous flow of the initial material and the intermittent flow of the accelerating liquid are contacted in the reaction or mixing device into which both streams are admitted separately through nozzles. The apparatus may also be provided with three pumps, one of these pumps inducing a continuous flow of the polyester component, another pump intermittently feeding the isocyanate component while the third pump intermittently feeds the activator component under high pressures.

An important feature of the invention resides in the manner in which the activator mixture is added to the remaining components used to form the plastics. The

activator mixture is forced into the polyester stream (mixed with the polyisocyanate if desired) at a relatively high velocity so that it will adequately penetrate the high viscosity polyester and form a uniform product. This is effected by means of an injection nozzle through which the activator mixture is. introducedat a pressure substantially in the range of about 300 p. s. i. to about 15,000 p. s. i. and preferably within the range of about 1200 p. s. i. to about 5250 p. s. i.

In its broadest aspect, the invention contemplates the use of injection pressures which are higher and preferably substantially higher than the back pressure within the reaction or mixing device. Normally, the back pressure within the device is of the order of from 45 p. s. i. to 75 p. s. .i. depending upon the viscosity of the material and the size of the discharge outlet. In the case of low viscosity materials, the back pressure may drop to as low as 17 p. s. i., but with more highly viscous materials, it may increase to much higher values than are normally encountered.

Thus, in the case of low viscosity materials, the injection pressure may fall as low as about 19 p. s. i. or in the case of moderately viscous materials it may drop to a value of about 47 p. s. i. to 77 p. s. i. Under these conditions substantially improved results over mechanical mixing are obtained, but such low pressures are not the equivalent of 300 p. s. i. and higher pressures since pressures of the latter order of magnitude result in more rapid and efficient mixing and products more uniform in texture and reproducible in character. Apparently there is no upper limit to the injection pressure that may be employed except that imposed by the equipment.

The injection nozzle also serves as a check valve since, when the pressure is lowered, the nozzle closes and the other reactants cannot back into the accelerator mixture feed line. Without such mechanical safeguard, the activator mixture feed line would quickly become blocked by solid material and the desired mixing operation could not be effected.

The invention will now further be described with referr ence to various forms of apparatus suitable for producing 7 porous and homogeneous plastics, which are illustrated in the accompanying drawings and in which v 'Fig. 1 1s a diagrammatic elevation of an apparatus for mixing the reaction mixture and activator,

'Figs. 2 and 3 are longitudinal sections through reactron devices,

Fig. 4 shows a diagrammatic elevation of an apparatus suitable for carrying out the modification of the process formixing two components of the reaction mixture and activator,

Figs. 5, 6 and 7 are longitudinal sections through relike.

Referring now to Fig. 1 an initial liquid reactant mixture of polyisocyanate and polyester, charged into tank 1, is passed to a gear pump 2 having a variable number of revolutions, which forces the reaction mixture at any desired rate through a reaction or mixing device 3 as illustrated in Figs. 2 or 3. This reaction or mixing device essentially consists of a feed pipe 5 for the reaction mixture and an injection nozzle 4 for the activator component through which the activator component is intermittently injected into the continuously flowing initial reaction mixture, either transversely to the flowing direction of the initial reactant mixture (see Fig. 3) or in counter-current to the initial reactant mixture (see Fig. 2). Injection in counter-current to the How of the initial reactant mixture, wherein the initial reactant mixture is preferably passed around the nose of the nozzle, has proved to be especially suitable. The injection impulses of the nozzle 4 are effected by the injection pump 6 (as shown in Fig. l), which is supplied with the activator component from the tank 7. After injection, the mixture is forced through a nozzle plate 52 into a cham her 8 into which a continuous compressed air stream is passed through a tangential air-pipe connection 9. The air stream effects an intense mixing of the reactive and expansible material, or the mixing operation is performed by means of a mechanically operating stirring equipment (see Figs. 5 and 7). In the tangential-transverse mixing operation shown in Fig. 3 the reaction mixture enters the ring chamber 54 through the feed pipe 5 and is then forced through the slots 55 to the mixing chamber 56, where intense mixing with the activator mixture intermittently injected through the nozzle 4 is effected. A second mixing operation by air or mechanically is not required.

The product, while still liquid, leaves the chamber in which the second mixing operation is carried out, and is cross-linked, rapidly or slowly, depending upon the character of the polyester-isocyanate-accelerator system employed, or is cross-linked and expanded. By suitable selection of the polyisocyanate-polyester mixture employed, the cross-linking and the blowing action can be accelerated in such a manner that cross-linked profile pieces or finished foamed plastics are promptly obtained after discharge of the mixture from the mixing chamber.

Fig. 4 shows an apparatus suitable for carrying out the modification of the process in which for instance a polyester containing hydroxyl groups, a diisocyanate and an activator component e. g. an accelerator and/ or crosslinking agent are all conveyed separately to the reaction or mixing device 10. The polyester is continuously fed from the storage tank 11 into the reaction or mixing device 10 by means of the pump 12 and, simultaneously but separately, a polyisocyanate is injected into the reaction or mixing device 10 from the storage tank 13 intermittently by means of the pump 14 and an activator from the storage tank 15 intermittently by means of the pump 16.

The reaction or mixing device 10 may be designed in various manners, for instance as shown in Figs. 5, 6, 7, 8 and 9. p

In the reaction or mixing device shown in Fig. 5, the components admitted through the nozzles 17, 18 and 19 are further mixed by means of the stirrer 20. The mixture thus obtained leaves the device through the outlet 21.

In the reaction or mixing device shown in Fig. 6 the components initially mixed by injection through the nozzles 22 and 23 and pipe 24 are finally mixed in the mixing or turbulence chamber 26 by means of a continuous air-current which is passed in tangentially through the pipe 25. The final mixture leaves the turbulence chamber through the outlet 27.

Fig. 7 shows a reaction or mixing device wherein the mixing operation is initially effected by injection, continued with a stirrer and completed by means of an air-current admitted tangentially. The components enter the injection chamber 51 separately through the nozzles 28, 29 and 30, they are further mixed in this chamber by means of the stirrer 31, forced through the nozzle plate 52 into the mixing or turbulence chamber 33, wherein they are finally mixed by the action of an air-current passed in through a tangential air-pipe connection 32, the mixture leaves the turbulence chamber 33 through the outlet 34.

Figs. 8 and 9 show two possible arrangements of the peripherally disposed nozzles 23, 29 and opening into the reaction device (shown in Fig. 7

Fig. 10 shows an apparatus for the manufacture of rigid and elastic polyurethane products, ,which enables block material to be produced in a continuous flow, or plastic or foamed plastic foils to be produced on a continuou sly travelling conveyor belt. Polyester is conveyed from a stationary tank 35 by means of the stationary pump 36 through a flexible tube 37 to a reaction or mixing device 38 (similar to numeral 10 in Fig. 4) mounted on a movable and oscillating carriage 39. A storage tank 40 for the isocyanate and a storage tank 41 for the accelerator mixture are mounted on the carriage 39. From the tank 40 the isocyanate is conveyed to the reaction of mixing device 38 by means of an injection pump 42, and from the tank 41 the accelerator mixture is conveyed to the reaction or mixing device 38 by means of an injection pump 43. For the production of foils, the final mixture issuing from the mixing chamber is deposited on a conveyor belt 44 arranged beneath the carriage 39 and slowly travelling transversely to the moving direction of the carriage 39.

The apparatus disclosed in Figure 10 is also adapted for use with a two-component feed system in the continuous manufacture of rigid and elastic polyurethane sheets or blocks or in the continuous production of plastic or foamed plastic foils on a continuously travelling conveyor belt. Using a two component system, the mixture of isocyanate and polyester, initially charged in tank 35, is continuously conveyed therefrom by means of a stationary dosing pump 36 through the flexible tube 37 to the reaction or mixing device 38 mounted on a movable and oscillating carriage 39. From the accelerator storage tank 41, also mounted on carriage 39, the accelerator mixture is conveyed and intermittently injected into the reaction device by means of the injection pump 43. For the production of foils, the final mixture issuing from the mixing chamber is deposited on the conveyor belt 44 arranged beneath the carriage 39, which slowly travels transversely to the moving direction of the carriage 39.

'Fig. 11 shows a device for producing moldings from foamed products, for instancev from polyurethanes. The mixture issuing from the reaction or mixing device 38 is cast into molds 45 which are arranged and positioned, preferably evenly spaced, on a turntable 47 driven by the engine 46.. The molds 45 are preferably filled at a rate so that the travelling motion of the molds is in proper relation to the rate of the mixture issuing from the reaction device 38.

Fig. 12 shows a device for producing for instance profile cords or cable coverings from materials having a basis of polyurethanes. After leaving the reaction device 38 the mixture is passed to or drops into a screw conveyor 48 which forces it through a mouth piece 53 provided with profile nozzles into a chamber 49 wherein the shaped article is hardened and then led to a roll 50 to be wound up.

The invention is further illustrated but not limited by thefollowing examples:

EXAMPLE 1 A mixture of 100 parts by volume of a polyester prepared from 16 mols of adipic acid, 16 mols of diethylene glycol and 1 mol of trimethylolpropane, and parts by volume of toluylene diisocyanate is charged into tank 1 (Fig. 1) and held at a temperature of 27 C. This mixture is fed continuously to the reaction or mixing device 3 at a rate of 2 liters per minute. The activator mixture consisting of 3 parts by volume of the adipic acid ester of N-diethylaminoethanol, 2 parts by volume of ammonium oleate and 1.2 parts by volume of water is stored in tank 7 at a temperature of 18 C. and intermittently injected into the stream of the polyester-isocyanate. mixture at a pressure increasing from 1,470 p. s. i. to 5,145 p. s. i. and at a rate of 0.08 liter per minute. This corresponds to a feed rate of 4 parts by volume of activator mixture for each 100 parts by volume of the isocyanatepolyester mixture and involves an injection rate of 1,500 injections per minute The temperature risesto 37 C. in the mixing chamber and during the foaming process, a temperature of about 100 C. is reached inside the foaming mass. The final elastic foam has a bulk density of 70-75 kg./m.

EXAMPLE 2 100 parts by volume of a polyester prepared from 16 mols of adipic acid, 16 mols of diethylene glycol and 1 mol of trimethylolpropane, held at a temperature of 22 C., 47 parts by volume of toluylene diisocyanate, held at a temperature of 18 C., and 10 parts by volume of an activator mixture as described below, held at a temperature of 18 C., are brought together using the apparatus diagrammatically represented by Fig. 4. The activator mixture consists of 3 parts by volume of the adipic acid ester of N-diethyl amino ethanol, 1 part by volume of ammonium oleate, 1.5 parts by volume of sulfonated castor oil, 1.5 parts by volume of water and 0.5 part by volume of a paratfin oil. The polyester is fed continuously to the reaction or mixing device 10 at a rate of 4 liters per minute, the diisocyanate at a rate of 2 liters per minute and the activator mixture at a rate of 0.4 liter per minute, respectively. The diisocyanate and the activator mixture are injected intermittently using 9,000 injections per minute and 3,000 injections per minute, re spectively. In the mixing chamber the temperature rises to 27 C. and in the foaming mass a temperature of 130 C. is reached. The final elastic foam has a bulk density, of kg./m.

EXAMPLE 3 A rigid foam with a bulk density of 75 kg./ m. is produced from the following mixture:

parts by weight of a polyester prepared from 2.5 mols of adipic acid, 0.5 mol of phthalic acid and'4 mols of trimethylol propane; 50 parts by weight of a polyester prepared from 3 mols of adipic acid,'1 mol of hexane- ;riol and 3 mols of 1.3-butylene glycol; and 10 parts by 10 weight of activated charcoal are mixed and hereinafter referred to as. polyester mixture. 1 part by volume of the adipic acid ester of N-dicthylaminoethanol, 1 part by volume of ammonium oleate and 2 parts by volume of sulfonated castor oil are mixed and hereinafter referred to as activator mixture.

parts by volume of the polyester mixture, 75 parts by volume of toluylene diisocyanate, and 4 parts by volume of the activator mixture, held at temperatures of 40 C., 18 C. and 18 C., respectively, are mixed by means of a reaction or mixing device diagrammatically represented in Fig. 4. To each 4.5 liters of polyester mixture passing each minute in continuous stream into the reaction or mixing device, 3.4 liters of toluylene diisocyanate and, separately, 0.18 liter of activator mixture are injected intermittently at a rate of 9,000 and 3,000 injections per minute, respectively. The temperature rises to 27 C. in the mixing chamber and to 180 C. in the foaming mass during the foaming process.

EXAMPLE 4 A rubber-like elastic polyurethane is obtained in the following way:

A mixture of 100 parts by volume of a polyester prepared from 11 mols of ethylene glycol and 10 mols of adipic acid with 25 parts by volume of 1.5-naphthalenediisocyanate is fed continuously at a temperature of C. and at a rate of 2 liters per minute to a mixing device 3 (Fig. 1). 2 parts by volume of butylene glycol are introduced into each parts by volume of the continuous stream of polyester-polyisocyanate mixture at a rate of 1,500 injections per minute, the butylene glycol serving as a cross-linking agent. The reaction mixture is cast at a temperature of C. into molds pre-heated to 100 C. The molding is then heated to 100 C. for 24 hours.

Where reference is made in the specification and claims to intermittently or intermittent feed, it is to be understood that these expressions are intended to designate an injection rate of about 50 to about 10,000 and preferably about 2,000 to about 10,000 injections per minutell]; and where reference is made to enclosed with respect to the vessel, device, mixer, or zone in which one or more of the components is injected into another one, or into an admixture of others, of the components, it is intended fo'designote that there are walls which embrace, encircle, or encompass, but do not necessarily totally envelop.

In addition to the various uses mentioned earlier herein, the products prepared by the process of the instant invention are useful in all of the applications set forth in application Serial No. 327,522.

We claim:

1. in a process for producing solid polyurethane plastics comprising bringing together in an enclosed mixing zone an organic compound having at least two reactive hydrogen atoms, said organic compound being capable of forming polyurethanes, a polyisocyauate and a component influencing the reaction leading to the formation of said solid polyurethane plastics, the improvement which comprises injecting at least one of the two last-mentioned components into said mixing zone intermittently at high frequency at a pressure substantially higher than that in said mixing zone and thereby effecting substantially instantaneous and intimate mixing of said components, and then discharging the resulting mixture While in a liquid state from said mixing zone into a zone where conversion of said liquid mixture into said solid polyurethane plastic takes place.

2. In a process for producing solid polyurethane. plastics comprising bringing together in an enclosed mixing zone an organic compound having at least two reactive hydrogen atoms, said organic compound being capable of forming polyurethanes, a polyisocyanate and a component influencing the reaction leading to the formation of said solid polyurethane plastics, the improvement which ously into said mixing zone, injecting said polyisocyanate into said mixing zone intermittently at high frequency at a pressure substantially higher than that in said mixing zone and thereby effecting substantially instantaneous and intimate mixing of said components, and then discharging the resulting mixture while in a liquid state from said mixing zone into a zone where conversion of said liquid mixture into said solid polyurethane plastic takes place. i

3. In a process for producing solid polyurethane plastics comprising bringing together in an enclosed mixing zone an organic compound having at least two reactive hydrogen atoms, said organic compound being capable of forming polyurethanes, a polyisocyanate and a compo nent influencing the reaction leading to the formation of said solid polyurethane plastics, the improvement which comprises introducing said organic compound and said polyisocyanate in admixture continuously into said mix ing zone, injecting said reaction-influencing component into said mixing zone intermittently at high frequency at a pressure substantially higher than that in said mixing zone and thereby elfecting substantially instantaneous and intimate mixing of said components, and then discharging the resulting mixture while in a liquid state from said mixing zone into a zone where conversion of said liquid mixture into said solid polyurethane plastic takes place.

4. In a process for producing solid polyurethane plastics comprising bringing together in an enclosed mixing zone an organic compound having at least two reactive hydrogen atoms, said organic compound being capable of forming polyurethanes, a polyisocyanate and a component influencing the reaction leading to the formation of said solid polyurethane plastics, the improvement which comprises introducing said organic compound continuously into said mixing zone, separately injecting each of the two last-mentioned components into said mixing zone intermittently at high frequency at a pressure substantially higher than that in said mixing zone and thereby effecting substantially instantaneous and intimate mixing of said components, and then discharging the resulting mixture while in a liquid state from said mixing zone into a zone where conversion of said liquid mixture into said solid polyurethane plastic takes place.

12 quency at the rate of about 50 to about 10,000 injections per minute and at a pressure substantially higher than thatin said mixing zone, said higher pressure being in-the range of about 300 to about 15,000 lbs. per sq. in., and

thereby effecting substantially instantaneous and intimate mixing of said components, and then discharging the resulting mixture while in a liquid state from said mixing zone into a zone where conversion of said liquid mixture'into said solid polyurethane plastic takes place.

7. In a'process for producing solid polyurethane plastics comprising bringing together in an enclosed mixing zone an organic compound having at least two reactive hydrogen atoms, said organic compound being capable of forming polyurethanes, a polyisocyanate and a component influencing the reaction leading to the formation of said solid polyurethane plastics, the improvement which comprises introducing said organic compound and said polyisocyanate in admixture continuously into said mixing zone, injecting said reaction-influencing component into said mixing zone intermittently at high frequency at the rate of about 50 to about 10,000 injections per minuteand at apressure substantially higher than that in said'mixing zone, said higher pressure being in the range of about 300m about 15,000 lbs. per sq. in., and thereby eflecting substantially instantaneous and intimate mixing of said components, and then discharging the'resulting mixture While in a liquid state from said mixing zone into a zone where conversion of said liquid mixture into said solid polyurethane plastic takes place.

8. In a process for producing solid polyurethane plastics comprising bringing together in an enclosed mixing zone an organic compound having at least two reactive hydrogen atoms, said organic compound being capable of forming polyurethanes, a polyisocyanate and a component influencing the reaction leading to the formation of said solid polyurethane plastics, the improvement which comprises introducing said organic compound continu- 5. In a process for producing solid polyurethane plastics comprising bringing together in an enclosed mixing zone an organic compound having at least tWo reactive r hydrogen atoms, said organic compound being capable of forming polyurethanes, a polyisocyanate and a component influencing the reaction leading to the formation of' said solid polyurethane plastics, the improvement which comprises injecting at least one of the two last-mentioned components into said mixing zone intermittently at high frequency at the rate of about 50 to about 10,000 injections per minute and at a pressure substantially higher than that in said mixing zone, said higher pressure being in the range of about 300 to about 15,000 lbs. per sq. in., and thereby effecting substantially instantaneous and intimate mixing of said components, and then discharging the resulting mixture while in a liquid state from said mixing zone into a zone where conversion of said liquid mixture into said solid polyurethane plastic takes place.

6. In a process for producing solid polyurethane plastics comprising bringing together in an enclosed mixing zone an organic compound having at least two reactive hydrogen atoms, said organic compound being capable of forming polyurethanes, a polyisocyanate and a component influencing the reaction leading to the formation of said solid polyurethane plastics, the improvement which comprises introducing said organic compound and said reaction-influencing component in admixture con tinuously into said mixing zone, injecting said polyisocyanate into said mixing zone intermittently at high fre til) ously into said mixing zone, separately injecting each of the two last-mentioned components into said mixing zone intermittently at high frequency at the rate of about 50 to about 10,000 injections per minute and at a pressure substantially higher than that in said mixing zone, said higher pressure being in the range of about 300 to about 15,000 lbs. per sq. in., and thereby effecting substantially instantaneous and intimate mixing of said components, and then discharging the resulting mixture while in a liquid state from said mixing Zone into a zone where conversion of said liquid mixture into said solid polyurethane plastic takes'place.

9. In a process for producing porous polyurethane plastics comprising bringing together in an enclosed mixing zone a polymeric material containing free hydroxyl groups, said polymeric material being capable of forming polyurethanes, a polyisocyanate and a water-containing component influencing the reaction leading to the formation of said porous polyurethane plastics, the improvement which comprises injecting at least one of the two last-mentioned components into said mixing zone intermittently at high frequency at a pressure substantially higher than that in said mixing zone and thereby effecting substantially instantaneous and intimate mixing.

of said components, and then discharging the resulting mixture while in a liquid state from said mixing zone into a zone where conversion of said liquid mixture into f said porous polyurethane plastic takes place.

10. In a process for producing porous polyurethane plastics comprising bringing together in an enclosed mixing zone a polymeric material containing free hydroxyl groups, said polymeric material being capable of forming polyurethanes, a polyisocyanate and a water-containing component influencing the reaction leading to the formation of said porous polyurethane plastics, the improvement which comprises introducing said polymeric material and said reaction influencing component in admixture continuously into said mixing zone, injecting said polyisocyanate into said mixing zone intermittently at high frequency at a pressure substantially higher than that in said mixing zone as; thereby elfecting substantially instantaneous and intimate mixing of said components, and then discharging the resultingmixture while in a liquid state from said mixing zone into a zone where conversion of said liquid mixture into said porous polyurethane plastic takes place.

11. In a process for producing porous polyurethane plastics comprising bringing together in an enclosed mixing zone a polymeric material containing free hydroxyl groups, said polymeric material being capable of forming polyurethanes, a polyisocyanate and a water-containing component influencing the reaction leading to the formation of said porous polyurethane plastics, the improvement which comprises introducing said polymeric material and said polyisocyanate in admixture continuously into said mixing zone, injecting said reaction-infiuencing component into said mixing zoneintermittently at high frequency at a pressure substantially higher than that in said mixing zone and thereby effecting substantially instantaneous and intimate mixing of said components, and then discharging the resulting mixture while in a liquid state from said mixing zone into a zone where conversion of said liquid mixture into said porous polyurethane plastic takes place.

12. in a process for producing porous polyurethane plastics comprising bringing together in an enclosed mixing zone a polymeric material containing free hydroxyl groups, said polymeric material being capable of forming polyurethanes, polyisocyanate and a water-containing component influencing the reaction leading the the formation of said porous polyurethane plastics, the improvement which comprises introducing said polymeric material continuously into said mixing zone, separately injecting each of the two last-mentioned components into said mixing zone intermittently at high frequency at a pressure substantially higher than that in said mixing zone and thereby effecting substantially instantaneous and intimate mixing of said components, and then discharging the resulting mixture while in a liquid state from said mixing zone into a zone Where conversion of said liquid mixture into said porous polyurethane plastic takes place.

13. A process as defined in claim 9 wherein the said high frequency is at the rate of about 50 to about 10,000 injections per minute, and the said higher pressures are in the range of about 300 to about 15,000 lbs. per sq. in.

14. A process as defined in claim 10 wherein the said high frequency is at the rate of about 50 to about 10,000 injections per minute, and the said higher pressures are in the range of about 300 to about 15,000 lbs. per sq. in.

15. A process as defined in claim 11 wherein the said high frequency is at the rate of about 50 to about 10,000 injections per minute, and the said higher pressures'are in the range of about 300 to about 15,000 lbs. per sq. in.

.16. A process as defined in claim 12 wherein thesaid high frequency is at the rate of about 50 to about10,000'

injections per minute, and the said higher pressures are in the range of about 300 to about 15,000 lbs. per sq. in.

17. In a process for producing solid polyurethane plastics comprising bringing together in an enclosed mixing zone an organic compound having at least two reactive hydrogen atoms, said organic compound being capable of forming polyurethanes, a polyisocyanate and a component influencing the reaction leading to the formation of said solid polyurethane plastics, the improvement which comprises injecting at least one of the two last-mentioned components into said mixing zone at a pressure substantially higher than that in said mixing zone and at least as uniformly as is obtained by intermittent injection at high frequency and thereby effecting substantially instantaneate mixing of said components, and then ischarging the resulting mixture While in a liquid state from said mixing zone into a zone where conversion of said liquidmixture into said solid polyurethane; plastic takes place.

18. In a process for protit. Ling solid polyurethane plastics comprising bringing together in an enclosed mixing zone an organic compound'having at least two reactive hydrogen atoms, said organic compound being capable of forming polyurethanes, a polyisocyanate and a compo-- nent influencing the reaction leadingto the formation of said solid polyurethane plastics, the improvement which comprises introducing said. organic compound and said reaction-influencing component in admixture continuously into said mixing-zone, injecting said polyisocyana'te into said mixing zone at a pressure substantially higher than that in said mixingzone and at least as uniformly as is obtained by intermittent injection at .highfrequency and thereby effecting substantially. instantaneous and intimixing of said. components, andv then discharging the resulting mixture while in a liquid state from said mixing zone into .a zone where conversion -.of said liquid mixture into said solid polyurethane plastic takesplace.

19. In a process for producing solid, polyurethane plastics comprising bringing together in an enclosed mixing zone anorganic compound having at leasttwo reactive hydrogen atoms, said organic compound being capable of forming polyurethanes, a polyisocyanate and a component influencing the reaction leading to the formation of said solid polyurethane plastics,.the improvement which comprises introducing said organic compound and said polyisocyanate in admixture continuously .into said mixing zone, injecting said reaction-influencing component into said mixing zone at a pressure substantially higher than that in said mixing zone and at least asuniformly as is obtained by intermittent injection at high frequency and thereby effecting substantially instantaneous and intimate mixing of said components, andv thendischarging the resulting mixture .while in a liquid state from said mixing zone into a zone .where conversion of said liquid mixture into said solid polyurethane plastic takes place.

20. In a process for producing solid polyurethane plastics comprising bringing together in an-enclosed mixing zone an organic compound having at least two reactive hydrogen atoms, said organic compound being capable of forming polyurethanes, a polyisocyanate and a component influencing the reaction leading to the formation of said solid polyurethane plastics, the improvement which comprises introducing said organic compound continuously into said mixing zone, separately injecting each of the two last-mentioned components into said mixing zone at a pressure substantially higher than that in said mixing zone and at leastas uniformly as is obtained by intermittent injectionat high frequency and thereby eiiecting substantially instantaneous and intimate mixing of said components, and thendischarging the resulting mixture While in a liquid state from said mixing zone into a zone where conversion of said liquid mixture into said solid polyurethane plastic takes place.

21. Ina process for producing solid polyurethane plastics comprising bringing together in an enclosed mixing zone an organic compound having at least two reactive hydrogen atoms, said organic compound being capable of forming polyurethanes, a polyisocyanate and a com.- ponent influencing the reaction leading to the formation of said solid polyurethane plastics, the improvement which comprises, introducing into said mixing zone an admixture composed of said organic compound and at least one of the two last-mentioned components, injecting the other one of said two last-mentioned components into said admixture in said mixing zone at a pressure substantially higher than that in said mixing zone and at least as uniformly as is obtained by intermittent injection at high frequency and thereby efiecting substantially instantaneous and intimate mixing of said components, and then discharging the resulting mixture while in a liquid state from said mixing zone into a zone where 15 conversion of said liquid mixture into said solid polyurethane plastic takes place.

22. The process of claim 21 wherein the component influencing the reaction is injected into said admixture.

23. The process of claim 21 wherein the polyisocyanate is injected into the admixture.

24. In a process for producing solid polyurethane plastics comprising bringing together an organic compound having at least two reactive hydrogen atoms, said organic compound being capable of forming polyurethanes, a polyisocyanate and a component influencing the reaction leading to the formation of said solid polyurethane plastics, the improvement which comprises, providing an admixture composed of said organic compound and one of said two last-mentioned components, introducing said admixture into a mixing zone, injecting the other one of the last two-mentioned components into said admixture in said mixing zone at a pressure substantially higher than that in said mixing zone and at least as uniformly as is obtained by intermittent injection at high frequency and thereby effecting substantially instantaneous and intimate mixing of said components, and then discharging the resulting mixture while in a liquid state from said mixing zone into a zone where conversion of said liquid mixture into said solid polyurethane plastic takes place.

25. The process of claim 24 wherein the admixture is composed of said organic compound and said reaction influencing component, and wherein the polyisocyanateis injected into said admixture.

26. The process of claim 24 wherein the admixture is composed of said organic compound and said p o-lyisocyanate, and wherein said component influencing the reaction is injected into said admixture.

27. In a process for producing solid polyurethane plastics comprising bringing together an organic compound having at least two reactive hydrogen atoms, saidorganic compound being capable of forming polyurethanes, a

polyisocyanate and a component influencing the reaction leading to the formation of said solid polyurethane plastics, the improvement which comprises, providing an admixture composed of said organic compound and one of said two last-mentioned components, introducing said admixture into an injection zone, injecting the other one of the last two-mentioned components into said adm ix-' ture in said injection zone at a pressure substantially higher than that in said injection zone and at least as uniformly as is obtained by intermittent injection at high frequency and thereby efiecting substantially instantaneous and intimate mixing of said components, and then removing the resulting mixture while still in a liquid state from said injection zone into a zone where conversion of said liquid mixture into said solid polyurethane palstic takes place.

28. In a process for producing solid polyurethane plastics comprising bringing together in an enclosed mixing zone a polyisocyanate modification of an organic compound having at least two reactive hydrogen atoms, said modified organic compound being capable of forming polyurethanes, and a water-containing component influencing the reaction leading to the formation of said ,zone at a pressure substantially higher than that in said -mixing zone and at least as uniformly as is obtained by intermittent injection at high frequency, and then discharging the resulting mixture while in a liquid state from said mixing zone into a zone where conversion of said liquid mixture into said solid polyurethane plastic takes place.

29. In a process for producing solid polyurethane plastics comprising bringing together in an enclosed mixing zone a polyisocyanate modification of an organic compound having at'least two reactive hydrogen atoms, said modified organic compound being capable of forming polyurethanes, and a component influencing the reaction leading to. the formation of said solid polyurethane plastics, the improvement which comprises substantially in stantaneously and intimately mixing said components, said mixing including the step of injecting the last-mentioned component into said mixing zone at a pressure substantially higher than that in said mixing zone and at least asuniformly as is obtained by intermittent injection at high frequency, and then discharging the resulting mixture while'in a liquid state from said mixing zone into a'zone where conversion of said liquid mixture into said solid polyurethane plastic takes place.

30. In a process for producing solid polyurethane plastics comprising bringing together in an enclosed mixing zone a compound selected from the group consisting of a polyisocyanate-modified polyester, a polyisocyanatemodified polyesteramide, a polyisocyanate-modified alkylene glycol, and a polyisocyanate-modified polyoxyalkylene glycol, said modified organic compound being capable of forming polyurethanes, and a' water-containing component influencing the reaction leading to the formation of said solid polyurethane plastics, the imas is obtained by intermittent injection at high frequency,

and then discharging the resulting mixture while in a liquid state from said mixing zone into a zone where conversion ofsaidliquid mixture into said solid polyurethane plastic takes place.

References Cited in the file of this patent or the original patent 2,451,715 Caldwell Oct. 19, 1948 2,527,689 Suthard et a1. Oct. 31, 1950 2,577,279 Simon et a1. Dec. 4, 1951 {2,577,281 Simon et a] Dec. 4, 1951. 2,676,157 1954 NeWell Apr. 20, 

